Ambiphilic Reactivity of a Ruthenaphosphaalkenyl:
Synthesis of P‑Pyrazolylphosphaalkene Complexes
of Ruthenium(0)

Trathen, Nicola; Greenacre, Victoria K.; Crossley, Ian R.; Roe, S. Mark

doi:10.1021/om4001988.s003

Ambiphilic Reactivity of a Ruthenaphosphaalkenyl: Synthesis of P‑Pyrazolylphosphaalkene Complexes of Ruthenium(0)

journal contribution

posted on 2013-05-13, 00:00 authored by Nicola Trathen, Victoria K. Greenacre, Ian R. Crossley, S. Mark Roe

The novel ruthenaphosphaalkenyl complex [Ru{PCH(SiMe₃)}Cl(CO)(PPh₃)₂], prepared from [RuHCl(CO)(PPh₃)₃] and Me₃SiCP, exhibits ambiphilic behavior, reacting at phosphorus with both nucleophiles and electrophiles. Its reaction with Li(pz′) or K[HB(pz′)₃] (pz′ = pz, pz*) affords [Ru{η¹-N:η²-P,C-P(pz′)CH(SiMe₃)}(CO)(PPh₃)₂], a rare example of a ruthenium(0) η²-phosphaalkene complex and the first example of a P-pyrazolylphosphaalkene. Conversely, reaction with the electrophilic PhHgCl leads to metalation at phosphorus, affording [Ru{η¹-P(HgPh)CH(SiMe₃)}Cl₂(CO)(PPh₃)₂].